Cationic emulsions of bituminous binders of the type bitumen/polymer and cationic emulsifying system preferably utilizable for obtaining said emulsions

ABSTRACT

This invention provides cationic emulsions of bituminous binders of the bitumen/polymer type, formed by a dispersion of an organic phase of the binder in an aqueous phase containing a cationic nitrogenous emulsifier and a mineral or organic acid, the acid being in appropriate quantity so that the pH of the aqueous phase is comprised between 3 and 9. The aqueous phase also contains an agent consisting of at least one water-soluble sequestering salt of phosphonic acid, particularly a salt of alkaline metal or of amine of hydroxyalkyl-1,1-diphosphonic acid, and optionally a water-soluble thickening agent. To obtain the emulsions, which are usable for road applications, the emulsifying agent, the sequestering agent and optionally the thickening agent may be used in the form of a premixture containing the agents and called cationic emulsifying system.

This is a division of application Ser. No. 932,502, filed Oct. 14, 1986,now U.S. Pat. No. 4,772,648. Priority is claimed under 35 USC 119 basedon French PCT/FR 86/00040 filed Feb. 12, 1986, based on French patentapplication No. 85,02211 filed Feb. 15, 1985, a certified copy of whichis of record in the file of the parent application Ser. No. 932,502.

FIELD OF THE INVENTION

The invention relates to cationic emulsions of bituminous binders of thebitumen/polymer type. In one aspect, the invention relates to a cationicemulsifying system preferably utilizable for obtaining these emulsions.

BACKGROUND OF THE INVENTION

Converting bituminous binders in cationic or anionic emulsions is awell-known technique. The emulsion consists of a dispersion of finebitumen globules in a continuous aqueous phase. The emulsion is calledanionic or cationic according to the total electrical charge surroundingthe globule which can be negative or positive. In the presence of acontinuous electric current, the micellae of bitumen of an emulsionsettle on the anode if the emulsion is anionic or on the cathode if theemulsion is cationic.

The conversion of bituminous binders to emulsion makes use ofemulsifying agents that favor the dispersion of the globules of binderin the aqueous phase by forming a charged protective shell that preventstheir agglomeration.

In the case of anionic emulsions, the emulsifying agent is of theanionic type and preferably consists of a fatty acid alkaline salt. Thisemulsifying agent is generally mixed with the bituminous binder in aquantity of from 0.05 to 2% by weight. The binder containing theemulsifying agent is then dispersed in an alkaline aqueous phase bypassing into an emulsifier.

Cationic emulsions are obtained by using cationic emulsifying agents,which generally consist of nitrogenized organic compounds such as fattyamines, fatty amidoamines, fatty imidoazolines, fatty mono anddiquaternary ammonium compounds and reaction products of one or more ofsaid products with ethylene or propylene oxide. The fatty radical of theemulsifying compounds can possess a very diversified chemical structureand the raw materials for the preparation of the emulsifying compoundscan originate from different sources such as animal fats, refinedpetroleum products, vegetable oils and liquid resins. The cationicemulsifying agent is generally dispersed in water to which hydrochloricacid is added. The hydrochloride formed is soluble. The homogeneoussolution thus obtained, having a pH generally comprised between 1 and 5,is then put into contact with the bituminous binder in an emulsifier inorder to form the emulsion.

Regardless of whether it is anionic or cationic, the emulsion isconsidered to be a means that allows lowering the viscosity ofbituminous binders. The emulsion restores, after rupture, the bituminousbinder to which has been added the emulsifying agent used for producingthe emulsion. The presence of this emulsifying agent in the bituminousbinder is regarded as exerting a favorable effect on the adhesiveness ofthe binder in the presence of mineral surface, provided it is within anarrow range of pH comprised between 1 and 6.

The largest sale of bituminous emulsions is mainly in the area ofbuilding and repair of roads, and essentially in the form of cationicemulsions. Experience in this field shows that cationic emulsions areeasier to apply and prevent the numerous inconveniences of anionicemulsions such as the possibility of restoration to emulsion in thepresence of water, of unforeseeable rupture in storage and of weakadhesiveness of the binder to the surface of the aggregate.

Cationic bituminous emulsions are mainly used according to two type oftechnique, namely, coating and encasing.

Coating consists in gluing layers of fine gravel on the surface of theroad by means of the bituminous emulsion in order to produce roughnessand make the surface impervious. This technique contributes to thecreation of a new runway layer.

In encasement, the bituminous emulsion allows the use of layers having athickness of from 0.4 cm to more than 20 cm, which integrate in alllevels of a road structure.

At present, due to the general reduction of budgets for repair andbuilding of roads, the use of the bitumen emulsion is particularlylimited to the repair of the surface of roads. However, due to theextreme mechanical demands to which are subjected the mosaics of thesurface coatings, the road bitumens of emulsifiable kinds do not havethe characteristics necessary that will allow them to bear thetangential stresses due to heavy loads and heavy traffic.

Under these circumstances, the bituminous binders exclusivelyconstituted of bitumen are being increasingly replaced by bituminousbinders of the bitumen/polymer type. The bitumen/polymer binders areproducts obtained from bitumens to which polymers have been added andhave eventually been modified by the latter. Optionally, a reagent suchas sulfur or a modifying agent and/or an adjuvant can also be present.

Examples of bituminous binders of the bitumen/polymer type comprisepreferably:

bitumens modified by olefinic polymers or by mixtures of fatty acids andhigher alcohols (French Pat. No. 7,627,936 [publication No. 2,364,960]of Sept. 17, 1976);

bitumens modified as above and on which have been grafted elastomers(French Pat. No. 7,627,937 [publication No. 2,364,961] of Sept. 17,1976);

bitumens modified by norbornene (French Pat. No. 7,630,316 [publicationNo. 2,367,102] of Oct. 8, 1976);

bitumens modified by dihalopolybutadienes serving as receptivestructures to block copolymers and to covulcanizable elastomers (FrenchPat. No. 7,806,160 [publication No. 2,418,812] of Mar. 3, 1978);

bitumens modified by block copolymers styrene/butadiene orstyrene/isoprene (French Pat. No. 7,639,233 [publication No. 2,376,188]of Dec. 28, 1976);

bitumens modified by block copolymers styrene/carboxylated diene(addition No. 7,831,689 [publication No. 2,440,967] of Nov. 9, 1978 toFrench Pat. No. 7,639,233);

bitumens modified by polyethylene waxes (French Pat. No. 7,729,953[publication No. 2,405,288] of Oct. 5, 1977);

bitumens modified by elastomeric acrylic polymers (French Pat. No.7,812,135 [publication No. 2,424,301] of April 25, 1978;

bitumens modified by polymers of the type polyvinyl alcohol, polyamide,polyester, polyurethane;

bitumens modified by olefinic copolymers, preferably among them,ethylene/propylene copolymers or ethylene/propylene/diene copolymers, orby copolymers of olefins and of vinyl monomers, preferablyethylene/vinyl acetate copolymers, ethylene/acrylic ester copolymers,ethylene/vinyl chloride copolymers;

bitumens modified by special polymers of the type of halogenatedpolymers and preferably fluorinated polymers such aspoly-tetrafluoroethylenes or fluorinated and chlorinated polymers, or ofthe type of silicon polymers such as polysiloxanes;

bituminous compositions obtained by bringing into contact one bitumenwith a mother solution containing one polymer, preferably one blockcopolymer styrene/conjugated diene and sulfur or a polysulfide oranother reactive agent, preferably vinyl monomer, as well as a petroleumfraction and/or a coal oil (French Pat. Nos. 7,818,534 [publication No.2,429,241] of June 21, 1978 and No. 8,210,095 [publication No.2,528,439] of June 10, 1982; French Pat. Nos. 7,910,987 [publication No.2,455,623] of May 2, 1979 and No. 8,216,433 [publication No. 2,533,935]of Sept. 30, 1982);

bitumens modified by a mixture of at least two of the polymers citedabove, and mixtures of said modified bitumens.

However, the emulsification of said different bitumens modified by theincorporation of polymers cannot be effected as such, since theimprovement on the properties of the bitumens systematically increasesthe viscosity of the medium, which hinders the preparation of bindersmodified by polymers making use of the conventional industrialequipments. Under these circumstances, it is necessary to use one orseveral fluidizing solvents, the main part they play being to reduce theviscosity of the medium and bring it to a range equivalent to that ofoperation of bitumens of penetration 80/100 and 180/220 between 100° C.and 150° C., that is, 1 to 10 poises. The solvent or solvents selectedhave among other properties that of being partially volatile whilepreserving the heavy fractions of plastifying and compatibilizingproperties between the polymer and the bitumen.

The applicant has observed that the formulation of emulsions of quickrupture from binders of the bitumen/polymer type fluidized or fluxed byoils of petroleum origin or resulting from the distillation of coal inthe presence of conventional cationic emulsifying agents such as thosementioned above, led to emulsions in which the rupture is poor oruncertain. It has been observed, on the other hand, that this rupturewas represented by a partial coagulation of the bitumen globules withoutever resulting in the first hours, even after several days, in the totalcoalescence of the micellae of the emulsion, and this, whatever the typeof emulsifying agent used and the concentration of said emulsifyingagent. This deficiency confers on the residual bituminous bindermechanical characteristics which are very inferior to those of theoriginal anhydrous bitumen/polymer binder. Therefore, it limits thedevelopment of the emulsions of bitumen/polymer binder in the field ofproducing thin and superficial coatings on roads having very heavytraffic. The applicant has demonstrated in addition that the phenomenonexclusively depended on a double interaction between the solvent and theemulsifying agent for a conventional emulsifying agent such as definedabove and between the solvent and the salts contained in the water,namely, alkaline earth salts and metallic salts. The nature of thebitumen and its origin, the type of polymer associated with the bitumen,and the presence of crosslinking or stabilizing reagent, on thecontrary, exert no influence on the phenomenon.

SUMMARY OF THE INVENTION

It has been found that the deletereous influence of the interactionsbetween solvent and emulsifying agent and between solvent and saltscontained in the water could be suppressed by using in the cationicemulsion of bitumen/polymer binder a specific emulsifying system thatresults from the association of at least one cationic nitrogenizedemulsifying agent with an adjuvant consisting of at least onewater-soluble sequestering salt of phosphonic acid.

Therefore, an object of the invention is to provide cationic emulsionsof bituminous binders of the bitumen/polymer type that are formed in adispersion of an organic phase consisting of the bitumen/polymer binderin an aqueous phase including a cationic nitrogenized emulsifying agentand an acid, the latter being present in an amount such that the pH ofthe aqueous phase has a value comprised between 3 and 9, the emulsionsbeing characterized by the fact that their aqueous phase also includesan adjuvant consisting of at least one water-soluble sequestration saltof phosphonic acid in which the sequestering power in relation to themetallic ions is equivalent, in a pH range of from 3 to 9, to a fixationof at least 5 mg calcium ions per gram of salt.

DETAILED DESCRIPTION OF THE INVENTION

The water-soluble sequestering phosphonic salt or salts are preferablyselected among the diphosphonic salts of the formula (I) ##STR1##wherein R₁ is a hydrocarbyl radical of C₁ to C₁₀, preferably an alkyl,cycloalkyl or aryl radical of C₁ to C₆, and the M symbols, which can beidentical or different, each designate a hydrogen atom or an M₁ group ina manner such that at least one M is an M₁ group the M₁ grouprepresenting one alkaline metal atom, the radical ##STR2## wherein thesymbols R₂ to R₄, which can be identical or different, each representsone hydrogen atom or an organic radical and in particular a hydrocarbylmonovalent radical of C₁ to C₈, preferably C₁ to C₆, and which mayinclude one or several functional groups and particularly an OH group,some of the R₂ to R₄ radicals can be combined to form a heterocycle withthe nitrogen atom to which they are bonded. The salts themselves are notemulsifying agents.

The alkaline metal that can represent the M₁ group is selected among themetals of group IA of the Periodic Classification of Elements such asshown in the HANDBOOK OF CHEMISTRY AND PHYSICS, 46th Edition, publishedby THE CHEMICAL RUBBER CO., the alkaline metal preferably consisting ofsodium or potassium.

The hydrocarbyl radicals eventually replaced by functional groups thatcan represent the symbols R₂ to R₄ are in particular alyl orhydroxyalkyl radicals of C₁ to C₈, preferably C₁ to C₆, such as methyl,ethyl, propyl, butyl, pentyl, hexyl, hydroxymethyl, hydroxyethyl,hydroxypropyl, or also cycloalkyl radicals of C₄ to C₈, preferablycyclopentyl or cyclohexyl, or aromatic radicals of C₆ to C₈ such asphenyl or tolyl.

When some of the R₂ to R₄ radicals are combined to form a heterocyclewith the nitrogen atom to which they are bonded, the heterocycle is inparticular aromatic and preferably of the pyridinic or alicyclic andpreferably of the piperidinic type.

The compounds of formula (I) are preferably the salts resulting from thereaction of the hydroxyhydrocarbyl-1,1-diphosphonic acid of formula (II)##STR3## with a compound selected among the hydroxides of the alkalinemetals of group IA of the Periodic Classification of Elements definedabove, anhydrous or hydrated ammonia, hydrazine and the amine of theformula ##STR4## wherein the symbols R₁ to R₄ having the meanings givenabove.

The concentration of the phosphonic salt water-soluble in the aqueousphase of the emulsion can vary widely according to the hardness of thewater used for producing the emulsion and/or the total content ofmetallic ions of this water. This concentration can advantageouslyrepresent 0.005% to 0.5% and preferably 0.01% to 0.3% by weight of theemulsion.

The cationic nitrogenized emulsifying agent present in the emulsion canconsist of one or several of the cationic nitrogenized emulsifyingagents known, the emulsifying agents can be preferably fatty monoamines,polyamines, amidoamines, amidopolyamines, salts or oxides of said aminesand amidoamines and reaction products of the above cited compounds withethylene oxide and/or propylene oxide. A general illustration ofcationic nitrogenized emulsifying agents among which can be selected theemulsifying agents utilizable according to the invention is given in themanual of KIRK-OTHMER entitled ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY,third edition, volume 22, pages 377 to 384.

According to an advantageous embodiment of the invention, the cationicnitrogenized emulsifying agent is formed by the association of one orseveral emulsifying agents A selected among the cationic nitrogenizedemulsifying agents of the type monoamines, diamines, amidoamines, oxidesof said amines or amidoamines, reaction products of said compounds withethylene and/or propylene oxide and quaternary ammonium salts with oneor several emulsifying agents B selected among the cationic nitrogenizedemulsifying agents possessing in their molecule at least threefunctional groups selected among the amines and amides groups in amanner such that one at least of said functional groups be an aminegroup, the weight ratio of the total quantity of the compound orcompounds A to the total quantity of A and B compounds being inparticular from 5% to 95%. This mode of operation results in an open andquick rupture of the emulsion which allows the bitumen/polymer binderimmediately to recover its initial properties.

The cationic nitrogenized emulsifying agent that can be used accordingto the invention can consist preferably of one or several cationicnitrogenized emulsifying agents selected among the following compounds:

fatty monoamines of formula (III) R₆ -NH2, wherein R₆ represents a fattyhydrocarbon radical and preferably an alkyl or alkenyl radical C₈ to C₂₂such as lauryl, stearyl, oleyl, and

polyamines and amidopolyamines of formula (IV)

    R--X(C.sub.n H.sub.2n)--NH.sub.2                           (IV)

wherein X represents a divalent group of the formula ##STR5## R is ahydrocarbyl radical and preferably alkyl or alkenyl having up to 22carbon atoms, preferably C₈ to C₂₂, m and n, which can be identical ordifferent, are integers of from 1 to 8, preferably from 1 to 6, p is anumber taking whole values of 0 to 6, preferably 0 to 3, r is equal to 0or 1 and q is an integer of from 2 to 10, preferably from 2 to 4. In themode of operation for which the cationic nitrogenized emulsifying agentincludes one or several cationic nitrogenized emulsifying agents Aassociated with one or several cationic nitrogenized agents B such asgenerally defined above, the emulsifying agents A can be in particularselected among:

the monoamines of formula (III)

the diamines and amidodiamines of formula (V)

    R--(CO).sub.r --NH--(C.sub.n H.sub.2n)--NH.sub.2           (V)

the amines of formula (VI) ##STR6##

the quaternary ammonium compounds of formula (VII)

    (R.sub.7).sub.j N.sup.+ (R.sub.8).sub.h Y.sup.-            (VII)

while the emulsifying agents B can in particular be selected among thepolyamines or amidopolyamines of formula (VIII)

    R--(CO).sub.r --NH--C.sub.m H.sub.2m --NH--(C.sub.n H.sub.2n)--NH.sub.2(VIII)

s representing in these formulae an integer from 1 to 6, preferably from1 to 3, the R₇ 's, which can be identical or different, designate C₆ toC₂₂ hydrocarbyl radicals which can be substituted with one or severalfunctional groups and preferably alkyl or alkenyl radicals from C₈ toC₂₂ or a benzyl radical, the R₈ 's, identical or different, representingalkyl radicals from C₁ to C₆, which can be hydroxylated, preferablymethyl, ethyl, propyl, hydroxyethyl, hydroxypropyl, Y⁻ designating ananion of a mineral acid, in particular a chloride anion, or of anorganic acid, preferably an acetate or formate anion, h being a numberequal to (4-j) and j being a number assuming the values 1, 2 or 3, whileR, r, m, n and q have the meanings given above.

The preferred cationic nitrogenized emulsifying agents that can be usedas emulsifying agents A have the following formulae ##STR7## R₉designating in these formulae an alkyl or alkenyl radical from C₁₂ toC₂₂, preferably stearyl and/or oleyl, R₁₀ designating an alkyl orhydroxyalkyl radical from C₁ to C₃, Y₁ ⁻ being a chloride or acetateanion, 1 being a number equal to (3-g) and g being a number assuming thevalues 1, 2 or 3 while r, j and h are numbers having the meanings givenabove.

Other preferred cationic nitrogenized emulsifying agents that can bepreferably used as emulsifying compounds B correspond to the followingformulae (XIII) and (XIV):

    R.sub.9 --NH--(CH.sub.2).sub.3 --.sub.f --NH.sub.2 and     (XIII)

    R.sub.9 --CO--NH--(CH.sub.2).sub.3 --.sub.f --NH.sub.2     (XIV)

wherein f designates a number assuming the values 2, 3, 4 or 5 and R₉has the above meaning.

The total quantity of cationic nitrogenized emulsifying agent in theemulsion can change widely. This quantity can advantageously representfrom 0.03% to 3%, preferably from 0.06% to 2%, of the total weight ofthe emulsion for obtaining emulsions of quick rupture and satisfactorystability.

The acids used for adjusting the pH of the emulsion to a value of from 3to 9 can be selected among the mineral acids of different degrees ofacidity or also among the mono- or polycarboxylic acids, saturated orunsaturated, and eventually hydroxylated which are defined in FrenchPat. No. 8,122,275 (publication No. 2,517,317) of Nov. 27, 1981.Preferred acids are hydrochloric, nitric, phosphoric, acetic, oxalic,citric and formic acids.

The bitumen-polymer binder reduced to cationic emulsion can be any oneof the products obtained from bitumens to which have been added one orseveral polymers and eventually modified by this or these polymer(s) inthe presence or absence of a reagent such as sulfur or an agent thatreleases sulfur such as a polysulfide, of a coupling or vulcanizationagent, it being likewise possible to add to said bitumens, if necessary,a fluxing agent such as a petroleum fraction, a coal oil, or a mixtureof said products.

Preferred bitumen/polymer binders can be selected among the differentbitumen/polymer binders cited above by way of example.

The emulsion according to the invention can also include a thickeningagent consisting of one or several water-soluble organic compounds,which, within a pH range of from 3 to 9, are capable of increasing theviscosity of the emulsion without modifying the viscosity of the aqueousphase alone containing the cationic nitrogenized emulsifying agent.

Among the compounds that can be used as thickening agents, there canpreferably be mentioned the water-soluble natural gums of the type guargum, arabic gum, ghatti gum, karaya gum, tragacanth gum, locust beangum, or also the water-soluble polyurethanes of low molecular weight,and in particular polyurethanes of molecular weight below 20,000 whichresult from the reaction of a polyisocyanate such as toluenediisocyanate, diphenyl methane 4,4'-diisocyanate, naphthylene1,5-diisocyanate, hexamethylene 1,6-diisocyanate, 3,3'-tolidene -4,4'-diisocyanate and m-phenylene disulphonyl diisocyanate with polyolsof the polyester polyol or polyether polyol type. As polyester polyolscan be mentioned the reaction products of a polycarboxylic acid such asadipic, phthalic or maleic acid with a polyol or a mixture of polyolssuch as ethylene glycol, propylene glycol, diethylene glycol,butanediol, glycerol, trimethylol propane, hexamethylene triol andpentaerythritol, while appropriate polyether polyols can be selectedamong the reaction products of polyols of the ethylene glycol, propyleneglycol, glycerol, trimethylol-propane, pentaerythritol, methylglycoside, sorbitol and sucrose type with epoxides of the ethyleneoxide, propylene oxide and epoxystyrene type.

The weight of thickening agent in the emulsion can advantageouslyrepresent from 5% to 30% of the total weight of the combination formedby the cationic nitrogenized emulsifying agent, the phosphonic adjuvantand the thickening agent.

The cationic emulsions according to the invention are prepared bymaking, in a zone of emulsion formation, particularly in an apparatus ofthe emulsifier type, a homogeneous dispersion of the bitumen/polymerbinder in an aqueous phase containing, in quantities adequate forobtaining the concentrations defined above, the emulsifying agentsalified by an acid in an amount sufficient for obtaining the desired pHvalue, the water-soluble phosphonic sequestering agent and optionallythe thickening agent. To do this, there are separately andsimultaneously brought to the zone of formation of the emulsion, on oneside, the bitumen/polymer binder in the form of a molten mass having atemperature between 80° C. and 180° C., preferably between 120° C. and160° C., and on the other hand, the aqueous phase containing the abovementioned ingredients and preferably between 20° C. and 60° C. and thecombination is maintained in said zone for a time sufficient for formingan emulsion.

The aqueous phase, which is mixed with the bitumen/polymer binder in thezone of formation of the emulsion, is prepared by introducing theemulsifying agent, the phosphonic sequestering compound, the acid andthe eventual thickening agent in the amount of water necessary forproducing the emulsion, which has been previously brought to atemperature comprised between 30° and 75° C. The quantities ofemulsifying agent, of phosphonic sequestering compound and of eventualthickening agent which are added to the water are selected in a mannersuch that the concentrations of said ingredients in the resultingemulsion be within the above defined ranges. The acid is used in aquantity sufficient for transforming, if necessary, the cationicemulsifying agent into a soluble salt and for bring the pH of theemulsion to the selected value. The ingredients, namely, cationicnitrogenized emulsifying agent, phosphonic sequestering compound, acidand thickening agent, can be added to the water in any order. Thephosphonic sequestering compound in particular can be introduced in thewater before or after salification of the emulsifying agent by the acid.The phosphonic sequestering compound can likewise be formed in situ inthe water from the corresponding precursor phosphonic acid and from abase apt to furnish salifying groups M₁ such as defined above.

In an advantageous form of preparation, at least the emulsifying agentand the phosphonic sequestering compound, or the phosphonic acidprecursor thereof, are simultaneously incorporated into the water in theform of a mixture called cationic emulsifying system which has beenpreviously made, the acid is then added and the thickening agent if itis used.

The cationic emulsifying system includes, therefore, a cationicnitrogenized emulsifying agent consisting of one or more cationicnitrogenized emulsifying agents and an adjuvant consisting of at leastone water-soluble phosphonic sequestering compound such as defined aboveor the phosphonic acid precursor thereof, said adjuvant being inparticular formed of at least one phosphonic compound selected among thecompounds of formula (I) or the phosphonic acids precursors thereof offormula (II).

In such an emulsifying system the weight of the cationic nitrogenizedemulsifying agent represents in particular from 10 to 99%, preferablyfrom 25 to 90%, of the total weight of emulsifying agent and adjuvant.

The cationic nitrogenized emulsifying agent present in the cationicemulsifying system can consist preferably of one or more of the cationicnitrogenized emulsifying agents selected among the fatty monoamines offormula (III) and the polyamines and amidopolyamines of formula (IV).

In a preferred manner of preparation, the cationic nitrogenizedemulsifying agent of the cationic emulsifying system is constituted bythe association of one or more cationic nitrogenized emulsifying agentsA with one or more cationic nitrogenized emulsifying agents B such asdefined above, the weight ratio of the total amount of the compound orcompounds A to the total amount of compounds A and B being in particularfrom 5 to 95%.

In particular the compounds A can be selected among the compoundsdefined above by formulae (III), (V), (VI) and (VII) and preferablyamong the compounds A defined by formulae (IX), (X), (XI) and (XII),while the B compounds can be selected among the compounds defined aboveby the formula (VIII) and preferably among the compounds B defined bythe formulae (XIII) and (XIV).

The cationic emulsifying system can also contain a thickening agentconsisting of one or more water-soluble organic compounds selected amongthose defined above, and in particular among the water-soluble naturalgums or among the water-soluble polyurethanes of low molecular weightand preferably those resulting from the reaction between apolyisocyanate and a polyol of the polyester polyol or polyether polyoltype.

The weight of thickening agent in the cationic emulsifying systemadvantageously represents from 5% to 30% of the total weight of themixture comprising the emulsifying agent, the phosphonic adjuvant andthe thickening agent.

In the preparation of the emulsion, the aqueous phase containing thecationic nitrogenized emulsifying agent, the phosphonic adjuvant, theacid and the thickening agent, on one hand, and the bitumen/polymerbinder, on the other, are brought to the zone of formation of emulsionin proportions such that the cationic emulsion resulting advantageouslycontains by weight from 30 to 85%, preferably from 50 to 80%, ofbitumen/polymer binder.

The cationic emulsions of bitumen/polymer binder according to theinvention are characterized by a quick and irreversible rupture uponcontact with the aggregates at the end of which the bitumen/polymerbinder immediately and entirely recovers it initial properties.

The emulsions according to the invention are particularly suited toapplications of road building and repair, to caulking in civilengineering or in construction and also to industrial uses.

The invention is illustrated by the examples that follow.

In these examples, which describe cationic emulsions of bituminousbinders prepared according to the prior art (control examples) andaccording to the invention, the quantities appearing below are given tocharacterize the samples of emulsion prepared:

medium diameter of the globular distribution of the bituminous binder,that is, the value of the diameter corresponding to the value of 50% onthe curve of cumulative gravimetric particle-size distribution of theglobules of the bituminous binder obtained by laser granulometricanalysis;

index of rupture in fine siliceous products (abbreviated IR) determinedaccording to the French standard NF T 66 017 and representing theminimum quantity, expressed in grams of siliceous sand of granulometryfrom 40 to 150 μm, entailing the rupture of 100 g of emulsion withformation of a bituminous clot sand/binder (a value of the rupture indexof about 80 corresponding to a quick rupture of the emulsion, which iswhat is sought);

time of rupture of the emulsion on plates of bituminous coatings withthe aid of microdorite fine gravel having a diameter of from 10 to 14 mm(on a surface formed by a bituminous coating the emulsion is placed,thereafter said emulsion is coated by means of fine gravel, and there iscounted from the time the emulsion is covered by the fine gravel, thetime that elapses until the rupture of the emulsion, which appears by anattachment of the fine gravel to the support).

Besides, the following characteristics have likewise been determined inthe course of the evaluation test of the rupture index:

quantity of liquid salted out after obtention of the clot of fine sandscoated by the bituminous binder ruptured and content of water of thisliquid (a small amount of liquid containing an elevated amount of waterresulting in a quick and open rupture of the emulsion); and

cohesion/elasticity of the clot of fine sands coated by the bituminousbinder since the formation of said clot, determined by traction testaccording to the French standard NF T 46 002.

The composition of the liquid, that is, of the water/emulsion phasesalted out during the rupture of the emulsion, objectively shows thequantity of non-ruptured emulsion, this information being related to thephenomenon of delay or arrest in the rupture of the emulsion. A smallamount of liquid containing an elevated amount of water corresponds to aquick and open rupture of the emulsion whereas a larger amount of liquidcontaining a small amount of water shows a slow rupture of the emulsion,which is what has to be prevented.

The immediate cohesiveness or elasticity of the clot of fine siliceoussands coated with bituminous binder is a characteristic that accountsfor the coalescence of the mass of globules of the ruptured bituminousbinder, and that gives an indication of the capacity of the bituminousbinder to recover its initial viscoplastic or elastomeric properties.

The emulsions described in the examples have been prepared using, as thecase may be, either city water having a total hardness corresponding toa hydrotimetric standard equal to 22° or an industrial water having atotal hardness corresponding to a hydrotimetric standard of 24° andcontaining 15 mg per liter of ferrous ions.

In the examples given below the quantities and percents are given byweight unless otherwise indicated.

EXAMPLE 1

In this example, which is a control example, there was prepared acationic emulsion at 70% of a bituminous binder consisting of anordinary bitumen of 180/220 penetration, as follows. There are formed inthe first place an aqueous phase consisting of an aqueous solution ofhydrochloride of the emulsifying agent, producing a 0.16% dispersion ofpropylene diamine-1,3 of tallow (cationic nitrogenized emulsifyingagent) in industrial water, thereafter adding to the dispersion 0.14%hydrochloric acid at 20° Be (d=1.16).

The emulsion was then produced in an emulsifier in which there weresimultaneously and separately introduced 100 parts of the aqueous phaseprepared as indicated above and brought to 45° C., and 700 parts of thebitumen brought to 145° C. There were obtained 1000 parts of a controlcationic emulsion the characteristics of which are given below:

PH: 3.5

medium diameter of the bitumen globules (μm): 3-5

index of rupture: 70

amount of salted out liquid after 1 hour (% of the emulsion): 6

amount of water in the salted out liquid (%): 95

cohesiveness of the clot: good

rupture time of the emulsion on coated plates (mn): about 30

The amount of salted out liquid is small, and it is essentially water.The time of rupture of the emulsion on coated plate is about 30 minutesfor a rupture index of 70. The cationic emulsion thus produced has abehavior deemed satisfactory with regard to the rupture phenomenon.

EXAMPLE 2

In this example, which represents a second control example, there wereprepared three cationic emulsions (tests I, II and III) at 70% of abituminous binder of the bitumen/polymer type constituted by a reactionproduct at elevated temperature of a road bitumen of 80/100 penetrationwith a mother solution consisting of a solution of sulfur and a blockcopolymer of styrene and butadiene, containing 25% styrene and 75%butadiene in a petroleum fraction obtained in refinery after catalyticcracking of the heavy distillates called "Light Cycle Oil", saidfraction having a distillation range on the order of from 180° C. to360° C.

For preparing the bitumen/polymer binder, the work was carried out asfollows. Twenty parts of block copolymer were dissolved in 80 parts ofthe petroleum fraction at a temperature comprised between 80° C. and100° C. After the polymer was completely dissolved, 0.6 part of sulfurwas added to the solution. Fifteen parts of the solution thus were mixedwith 85 parts of the road bitumen and the mixture was brought to atemperature comprised between 170° C. and 180° C. for about 1.5 hours.There was thus obtained a bitumen/polymer binder, the maincharacteristics of which are indicated herebelow.

    ______________________________________                                        viscosity at 160° C.                                                                         89 mPa.s                                                pseudo-viscosity at 50° C. with                                                              115 seconds                                             an orifice of 10 mm (NF T 66 005)                                             traction test at - 10° C. with                                         a speed of 500 mm/mn                                                          ______________________________________                                    

Stress at threshold: 5.7×10⁵ Pa

Stress at breakage; 1.07×10⁵ Pa

Elongation at threshold: 20%

Elongation at breakage: >900%

The bitumen polymer binder was emulsified by the following procedure.

There are formed in the first place an aqueous phase consisting of anaqueous solution of hydrochloride of the emulsifying agent, producing adispersion of propylene diamine-1,3 of tallow (cationic nitrogenizedemulsifying agent) in industrial water, thereafter adding to thedispersion 0.14% hydrochloric acid at 20° Be.

Percentages in the aqueous phase of the amounts of emulsifier andhydrochloric acid employed, represented respectively,

0.15% and 0.14% for case I; 0.25% and 0.21% for case II and 0.08% and0.06% for case III.

The emulsion was then produced in an emulsifier in which there weresimultaneously and separately introduced 300 parts of the aqueous phaseprepared as indicated above and brought to 45° C., and 700 parts of thebitumen brought to 145° C.

There were obtained 1000 parts of control cationic emulsions of whichthe characteristics are given below:

    ______________________________________                                        Test              I        II       III                                       ______________________________________                                        pH                3.5      4        4.2                                       medium diameter of the globules                                                                 3-5      3-5      3-6                                       of binder (μm)                                                             rupture index     5O       8O       4O                                        quantity of salted out liquid                                                                   35       21       45                                        after 1 hour (% of the emulsion)                                              quantity of water in the                                                                        32       60       32                                        salted out liquid (%)                                                         cohesiveness of the clot                                                                        zero     zero     zero                                      time of rupture of the emulsion                                                                 >180     >180     >180                                      on plates of coated products (mn)                                             ______________________________________                                    

in the three tests all the bitumen/polymer binder is emulsified and thecationic emulsions produced have a good stability in storage.

On the other hand, although in the three emulsions the values of theindex of rupture were from quick to very quick ruptures, the quantity ofsalted out liquid in the test for determining said index is considerableand this liquid contains a high rate of non-ruptured emulsions. Besides,the clot of the mixture of sand and bitumen/polymer binder formed afterrupture of the emulsion shows no cohesiveness and in addition the timeof rupture of the emulsion on plates of coated material is considerablein each case.

ExAMPLES 3 to 5

In these examples cationic emulsions according to the invention wereprepared with 70% of a bituminous binder of the bitumen/polymer typeidentical with the one described in Example 2.

The bitumen/polymer binder was emulsified using the mode of operationthat follows.

There was first formed an aqueous phase consisting of an aqueoussolution of the hydrochloride of the emulsifying agent by producing adispersion of the emulsifying agent in industrial water (Example 3) orin city water (Examples 4 and 5), and then adding to the dispersion,counted in percents of the aqueous phase, 0.13% of hydrochloric acid of20° Be, then 0.2% of an aqueous solution with 40% tetrapotassium salt ofhydroxypropane-1,1 diphosphonic acid.

The emulsifying agent used consisted of a mixture of tallow propylene -1,3 diamine (emulsifying agent of type A) and of a tallow polypropylenepolyamine sold under the name of LILAMULS EM30 (emulsifying agent oftype B) in quantities respectively representing, in percents of theaqueous phase, 0.015% and 0.135% in Examples 3 and 4, and 0.16% and0.02% in Example 5. The aqueous phase obtained in each case was limpid.

The emulsion was then produced in an emulsifier in which there weresimultaneously and separately introduced 300 parts of the aqueous phaseprepared as indicated above and brought to 45° C. and 700 parts of thebitumen/polymer binder brought to 145° C.

In each example there were obtained 1000 parts of cationic emulsions,the characteristics of which are given herebelow.

    ______________________________________                                        Example           3        4        5                                         ______________________________________                                        pH                5        5.2      5.3                                       medium diameter of the                                                                          4-7      3-6      3-7                                       binder globules (μm)                                                       rupture index     6O       6O       65                                        amount of salted out liquid                                                                     7        7        9                                         after 1 hour (% of the emulsion)                                              amount of water in the salted out                                                               95       95       97                                        liquid (%)                                                                    cohesiveness of the clot                                                                        strong   strong   strong                                                      elasticity                                                                             elasticity                                                                             elasticity                                time of rupture of the emulsion                                                                 30-60    30-60    30-60                                     on plates of coated products (mn)                                             ______________________________________                                    

For the three examples all the bitumen/polymer binder was emulsified andthe stability in storage of the emulsions produced is good.

The rupture indices of the emulsions are low, and there was found abehavior of the emulsions similar to that of an ordinary bitumenemulsion, namely, small amount of salted out liquid phase and smallamount of non-ruptured emulsion.

Besides, the clot of sand and bitumen/polymer obtained in the course ofthe test for determining the rupture index showed a strongcohesiveness-elasticity and can be subjected to a characterization bytraction test.

Herebelow are given the traction characteristics of the clot resultingfrom the rupture of the emulsion of Example 3 in the course of the testfor determining the rupture index, the traction test having been carriedout according to the standard NF T 46 002, working at 0° C. with atraction speed of 500 mm/mn.

Stress at threshold: 2.55×10⁵ Pa

Stress at breakage: 0.68×10⁵ Pa

Elongation at threshold: 15%

Elongation at breakage: 570%

EXAMPLE 6

There was prepared a cationic emulsion of a bituminous binder of thebitumen/polymer type obtained as described in Example 2, but replacingthe petroleum fraction "Light Cycle Oil" by the same amount of ananthracenic coal oil having a distillation range on the order of from200° to 400° C.

The emulsion was prepared as follows:

There was first formed an aqueous dispersion of emulsifying agent bydispersing in industrial water a mixture of cationic nitrogenizedemulsifying agents consisting of stearic propylene amidoamine(emulsifying agent of type A) and an alkyl amidopolyamine sold under thename of EMULSAMINE L 60 (emulsifying agent of type B), said emulsifyingagents being used in amounts respectively representing 0.02% and 0.15%of the aqueous dispersion. There were then introduced in to thedispersion, expressed in percents of the latter, 0.2% of an aqueoussolution with 40% of tetrapotassium salt of hydroxypropane-1,1diphosphonic acid and then 0.25% of an acetic acid solution at 96%(density =1.06). There was obtained a limpid aqueous phase.

In the emulsifier there was separately and simultaneously introduced 300parts of the aqueous phase prepared as indicated above and brought to45° C. and 700 parts of the bitumen/polymer binder brought to 145° C.

There were obtained 1000 parts of cationic emulsion having thecharacteristics given herebelow.

PH: 5.6

medium diameter of the globules of binder (μM): 3-6

rupture index: 60

quantity of liquid salted out after 1 hour (% of the emulsion): 6

quantity of water in the salted out liquid (%): 98

cohesiveness of the clot: great elasticity

time of rupture of the emulsion on plates of coated product (mn): 301460

The whole binder is emulsified and the stability in storage of theemulsion produced is good.

The rupture index of the emulsion is low and the rupture of the emulsionis accompanied by the salting out of a reduced amount of liquidcontaining little of the non-ruptured emulsion. Besides, the clot ofsand and bitumen/polymer binder obtained in the course of the test fordetermining the index of rupture has a strong cohesiveness-elasticity.

EXAMPLE 7

There was prepared a cationic emulsion of a bituminous binder of thebitumen/polymer type obtained by mixing a road bitumen of 80/100penetration with a ethylene/vinyl acetate copolymer containing 45% vinylacetate. The binder was prepared by dispersing, by stirring and forabout 2 hours, 50 parts of the copolymer in 950 parts of the bitumenbrought to 180° C., then fluidizing the homogeneous solution obtained byadding 10% of an anthracenic coal oil having a distillation range on theorder of from 200° to 300° C. The main characteristics of the binderobtained are indicated herebelow:

viscosity at 160° C.: 0.97 mPa.s

pseudo-viscosity at 50+ C. with an orifice of 10 mm (NF T 66 005): 128seconds

traction test at -10° C. with a speed of 500 mm/mn

Stress at threshold: 12.3×10⁵ Pa

Stress at breakage: 6.3×10⁵ Pa

Elongation at threshold: 15%

Elongation at breakage: 320%

The binder was emulsified by following the mode of operation describedin Example 6.

There were obtained 1000 parts of cationic emulsion of bitumen/polymerbinder having the characteristics given herebelow.

pH: 5.5

medium diameter of the globules of binder (μm): 3-6

rupture index: 58

quantity of salted out liquid after 1 hour (% of the emulsion): 6

quantity of water in the salted out liquid (%): 99

cohesiveness of the clot: strong cohesiveness

time of rupture of the emulsion on plates of coated product (mn): 30-60

All of the binder is emulsified during the preparation of the emulsionand the stability in storage of the emulsion produced is good.

The rupture index of the emulsion is low and the rupture of the emulsionis accompanied by the salting out of a reduced amount of liquidcontaining very little of the non-ruptured emulsion. Additionally, theclot of sand and bitumen/polymer binder obtained in the course of thetest for determining the rupture index has a strong cohesiveness.

EXAMPLE 8

There were prepared two cationic emulsions of a bituminous binder of thebitumen/polymer type obtained by mixing a road bitumen of penetration80/100 with a stellate triblock copolymer styrene/butadiene/styrene soldunder the name of SOLPRENE 411 by PHILLIPS PETROLEUM. The binder wasprepared by dispersing, by stirring for 2 hours, three parts of thecopolymer in 100 parts of the bitumen brought to 180° C., thenfluidizing the homogeneous solution obtained by adding 12% of apetroleum fraction of the "light Cycle Oil" type having a range ofdistillation of from 180° C. to 360° C. The main characteristics of thebinder obtained are given herebelow:

viscosity at 160° C.: 102 mPa.s

pseudo-viscosity at 50° C. with an orifice of 10 mm (NF T 66005): 132seconds

traction test at -10° C. with a traction speed of 500 mm/mn

Stress at threshold: 7.1×10⁵ Pa

Stress at breakage: 0.05×10⁵ Pa

Elongation at threshold: 20%

Elongation at breakage: 800%

The bitumen/polymer binder was emulsified by making use either of theprocedure of example 6 according to the invention (test 8.1) or of theprocedure of the control Example 2 (test 8.II).

In each case there were obtained 1000 parts of a cationic emulsion ofthe bitumen/polymer binder having the characteristics stated herebelow:

    ______________________________________                                        test                 8.I      8.II                                            ______________________________________                                        pH                   5.4      3.7                                             medium diameter of the globules                                                                    4-7      3-6                                             of binder (μm)                                                             rupture index        6O       63                                              quantity of liquid salted out                                                                       7       33                                              after 1 hour (% of the emulsion)                                              quantity of water in the                                                                           95       32                                              salted out liquid (%)                                                         cohesiveness of the clot                                                                           strong   zero                                                                 elasticity                                               time of rupture of the emulsion                                                                    30-60    >180                                            on plates of coated product (mn)                                              ______________________________________                                    

In each one of the tests all of the binder was emulsified during thepreparation of the emulsion and the stability in storage of the emulsionproduced is good.

For the emulsion of test 8.I according to the invention the ruptureindex of the emulsion is low and the rupture of the emulsion isaccompanied by salting out of reduced amount of liquid containing verylittle of non-ruptured emulsion. Besides, the clot of sand andbitumen/polymer binder obtained in the course of the test fordetermining the rupture index has a strong elasticity.

The traction characteristics of this clot obtained by traction testfollowing the standard NF T 46002 working at 0° C. with a traction speedof 500 mm/mn are the following:

Stress at threshold: 3.05×10⁵ Pa

Stress at breakage: 0.38×10⁵ Pa

Elongation at threshold: 15%

Elongation at breakage: 180%

For the control emulsion of test 8.II, the rupture index has a valueapproximate to that of the emulsion of test 8.I, but the rupture of theemulsion is accompanied by the salting out of a considerable amount ofliquid containing a great proportion of non-ruptured emulsion. Inaddition, the clot of sand and bitumen/polymer binder obtained in thecourse of the test for determining the rupture index has no cohesivenessat all. Finally, the time of rupture of the emulsion on plates of coatedproducts is much longer than that measured for the emulsion of test 8.Iaccording to the invention.

EXAMPLE 9

A bituminous binder of the bitumen/polymer type was prepared by mixing80 parts of a road bitumen of penetration 80/100 brought to 180° C. with20 parts of a vulcanized mother solution formed from a hydrocarbonsolvent, a block copolymer of styrene and butadiene and sulfur asindicated in French Pat. No. 7,910,987 (Publication No. 2,455,623) ofMay 2, 1979.

The bitumen/polymer binder obtained had the following characteristics:

viscosity at 160° C.: 0.60 mPa.s

pseudo-viscosity at 50° C. with an orifice of 10 mm (NF T 66 005): 78seconds

traction test at 0° C. with a traction speed of 500 mm/mn

Stress at threadhold: 2,55×10⁵ pa

Stress at breakage: 0,14×10⁵ Pa

Stress at threshold: 2.55×10⁵ Pa

Stress at breakage: 0.14×10⁵ Pa

Elongation at threshold: 15%

Elongation at breakage: >900%

From the bitumen/polymer binder thus obtained, there were prepared twocationic emulsions by making use either of the procedure of example 6(test 9.I) or of the procedure of the control Example 2 (test 9.II) Ineach case there were obtained 1000 parts of a cationic emulsion of thebituminous binder of the bitumen./polymer type having the followingcharacteristics:

    ______________________________________                                        test                9.I        9.II                                           ______________________________________                                        pH                  5.5        3.8                                            medium diameter of the globules                                                                   3-6        3-6                                            of binder (μm)                                                             rupture index       57         58                                             quantity of liquid salted out                                                                      6         37                                             after 1 hour (% of the emulsion)                                              quantity of water in the liquid                                                                   97         32                                             salted out (%)                                                                cohesivesness of the clot                                                                         good       zero                                                               cohesiveness                                              time of rupture of the emulsion                                                                   30-60      >180                                           on plates of coated product (mn)                                              ______________________________________                                    

In each one of the tests all of the binder is emulsified during thepreparation of the emulsion and the stability in storage of the emulsionobtained is good.

For the emulsion of test 9.I according to the invention the ruptureindex of the emulsion is low and the rupture of the emulsion isaccompanied by salting out of a reduced amount of liquid containing verylittle of non-ruptured emulsion. Additionally, the clot of sand andbitumen/polymer binder obtained in the course of the test fordetermining the rupture index has a good cohesiveness.

The traction characteristics of this clot obtained by traction testaccording to standard NF T 46002, working at 10° C. with a tractionspeed of 500 mm/mn are the following:

Stress at threshold: 3.3×10⁵ Pa

Stress at breakage: 0.27×10⁵ Pa

Elongation at threshold: 10%

Elongation at breakage: 230%

For the control emulsion of test 9.II, the rupture index has a valuecomparable to that of the emulsion of test 9.I, but the rupture of theemulsion is accompanied by salting out of a considerable amount ofliquid containing a substantial proportion of non-ruptured emulsion.Besides, the clot of sand and bitumen/polymer binder obtained in thecourse of the test for determining the rupture index has no cohesivenessat all. Finally, the time of rupture of the emulsion on plates of coatedproduct is much longer than that measured for the emulsion of test 9.Iaccording to the invention.

EXAMPLE 10

From the bitumen/polymer binder obtained as described in Example 2,there was prepared a cationic emulsion according to the invention with70% of said binder following the mode of operation defined in Example 5,but with two modifications, namely, the use by way of emulsifying agentof a mixture of dimethyl benzyl ammonium tallow chloride sold under thename of NORAMIUM S 75 by the firm CECA and of tallow polypropylenepolyamine (LILAMULS EM 30) in respective quantities representing 0.17%and 0.1% of the aqueous phase, and the use of an amount of hydrochloricacid representing only 0.1% of the aqueous phase.

There were obtained 1000 parts of cationic emulsion having the followingcharacteristics:

PH: 5.6

medium diameter of the globules of binder (μm): 3-6

rupture index: 50

quantity of liquid salted out after 1 hour (% of the emulsion): 10

quantity of water in the liquid salted out (%): 97

cohesiveness of the clot: great elasticity

time of rupture of the emulsion on plates of coated product (mn): 30-60

All of the bitumen/polymer binder was emulsified and the stability instorage of the emulsion produced is good.

The rupture index of the emulsion is low and there is found a behaviorof the emulsion similar to that of an ordinary bitumen, namely, smallamounts of salted out liquid phase and little of non-ruptured emulsion.

Besides, the clot of sand and bitumen/polymer binder obtained in thecourse of the test for determining the rupture index has a strongcohesiveness-elasticity characterized by traction test.

EXAMPLE 11

From the bitumen/polymer binder obtained as described in Example 2,there was prepared a cationic emulsion according to the invention with70% of said binder as follows.

There was first formed a mixture of 45 parts of dimethyl benzyl ammoniumtallow chloride (NORAMIUM S 75), 25 parts of tallow polypropylenepolyamine (LILAMULS EM 30), 25 parts of an aqueous solution with 40%tetrapotassium salts of hydroxypropane-1, 1-diphosphonic acid and 67parts of an aqueous solution with 30% of a thickening agent consistingof arabic gum.

An aqueous phase was prepared by incorporating 0.4 part of the mixturethus produced into 100 parts of city water and then adding to thedispersion 0.1 part of hydrochloric acid at 20° Be.

The emulsion was then produced in an emulsifier in which weresimultaneously and separately introduced 300 parts of the aqueous phaseprepared as indicated above and brought to 45° C. and 700 parts of thebitumen/polymer binder brought to 145° C.

The cationic emulsion obtained had characteristics similar to those ofthe cationic emulsion obtained in example 10 although its viscosity washigher, namely, above 100 centistokes.

All of the bitumen/polymer binder was emulsified and the stability instorage of the emulsion produced was good.

What is claimed is:
 1. A cationic emulsifying system which contains acationic nitrogen containing emulsifying agent consisting essentially ofat least one cationic nitrogen-containing emulsifying agent and anadjuvant consisting essentially of at least one water-solublesequestering salt of phosphonic acid or the acid precursor of said salt,said salt having a sequestration power in respect to the metallic ionsthat is equivalent, within the pH range of from 3 to 9, to a fixation ofat least 5 mg of calcium ions per gram of salt and having the formula##STR8## wherein R¹ represents a hydrocarbyl radical group having fromC₁ to C₁₀, and each M, which can be identical or different, designates ahydrogen atom or an M₁ group and wherein at lest one M group comprises aM₁ group, said M₁ group representing a member selected from the groupconsisting of alkali metal atoms, a radical --NH₃ --NH₂ and a radical ofthe formula ##STR9## wherein R₃ and R₄, can be identical or different,and each represents a hydrogen atom or a hydrocarbyl monovalent radicalhaving from C₁ to C₈, which can be substituted with functional groupsand wherein two of R₃ and R₄ can form a heterocycle with the nitrogenatom to which they are bonded, the weight of cationic emulsifying agentrepresenting from about 10% to about 99% of the total weight ofemulsifying agent and phosphonic adjuvant.
 2. An emulsifying systemaccording to claim 1 wherein Ra and Ra are hydrocarbyl radicals of fromC₁ to C₆ and said alkali metal atom is sodium or potassium.
 3. Anemulsifying system according to claim 1, wherein R₁ is an alkyl, aryl,or cycloalkyl radical.
 4. An emulsifying system according to claim 1wherein the hydrocarbyl radicals that can represent the symbols R₂ to R₄are alkyl or hydroxyalkyl radicals from C₁ to C₈, cycloalkyl radicalsfrom C₄ to C₈, or aromatic radicals from C₆ to C₈, and wherein some ofthe R₂ to R₄ radicals can form an aromatic or alicyclic heterocycle withthe nitrogen atom to which they are bonded heterocycle, with thenitrogen atom to which they are bonded.
 5. An emulsifying systemsaccording to claim 4 wherein said R₂ to R₄ are from C₁ to C₆.
 6. Anemulsifying system according to claim 1 wherein the emulsifying agentrepresents from 25 to 90% of the total weight of emulsifying agent andphosphonic adjuvant.
 7. An emulsifying system according to claim 1wherein the cationic nitrogen containing emulsifying agent comprises atleast one cationic nitrogen containing emulsifying agent selected fromthe group consisting of fatty monoamines, polyamines, amidoamines,amidopolyamines, salts or oxides of said amines and amidoamines andreaction products of said compounds with ethylene and/or propyleneoxide.
 8. An emulsifying system according to claim 1 wherein thecationic nitrogen containing emulsifying agent consists essentially ofat least one cationic nitrogen containing emulsifying agent selectedfrom the group consisting of fatty monoamines of the formula R₆ -NH₂,wherein R₆ represents a fatty hydrocarbon radical selected from alkyl oralkenyl radicals having from C₈ to C₂₂ and polyamines andamiodopolyamines of the formula

    R--X--(C.sub.n H.sub.2n)--NH.sub.2

wherein X represents a bivalent group of the formula ##STR10## wherein Ris a hydrocarbyl radical, having up to 22 carbon atoms, m and n, can beidentical or different, and are integers from 1 to 8, p has a value offrom 0 to 6, r is 0 to 1 and q is an integer from 2 to
 10. 9. Anemulsifying system according to claim 8 wherein R is alkyl or alkenyl offrom C₈ to C₂₂ ; m and n are integers of from 1 to 6; p has a value offrom 0 to 3; and q is an integer of from 2 to
 4. 10. An emulsifyingsystem according to claim 1 wherein the cationic nitrogen containingemulsifying agent is formed by association of at least one emulsifyingagent A selected from the group consisting of monoamines, diamines,amidoamines, oxides of said amines and amidoamines, reaction products ofsaid compounds with at least one of ethylene oxide and propylene oxideand quaternary ammonium salts with at least one emulsifying agent R₁ isselected from the group consisting of cationic nitrogen containingemulsifying agents having in their molecule at least three functionalgroups selected from the group consisting of amine and amide groups in amanner such that at least one of said functional groups is an aminegroup.
 11. An emulsifying system according to claim 10, wherein theweight ratio of the total quantity of the compound B or the compounds Ato the total quantity of the Compounds A and B is from 5% to 95%.
 12. Anemulsifying system according to claim 10 wherein the emulsifying agent Acomprises at least one member selected from the group consistingofmonoamines of formula R₆ NH₂, diamines and amidoamines of the formula

    R--(CO).sub.r --NH--(C.sub.n H.sub.2a)--NH.sub.2),

amines of the formula ##STR11## and quaternary ammonium compounds of theformula (R₇)_(J) N⁺ (R₈)_(h) y- and the emulsifying agent B comprises atleast one member selected from the group consisting of polyamines andamidopolyamines of the formula

    R--(CO)r--NH--C.sub.m H.sub.2m --NH.sub.s --(C.sub.n H.sub.2n)--NH.sub.2

wherein R represents a hydrocarbyl radical, having up to 22 carbonatoms, m and n, can be identical or different, being integers from 1 to8, r is 0 to 1, q is an integer from 2 to 10, s is an integer from 1 to6, and each R₇, can be identical or different, and designate a C₆ to C₂₂hydrocarbyl radical which can be substituted with one or more functionalgroups, said hydrocarbyl radicals being selected from alkenyl or alkylradicals of from C₆ to C₂₂ or a benzyl radical, each R₈ can be identicalor different and represents alkyl or hydroxyalkyl radicals having fromC₁ to C₆,Y⁻ is an anion of a mineral or organic acid, h is a numberequal to (4-j) and j is a number having a value 1,2, or
 3. 13. Anemulsifying system according to claim 12 wherein R is alkyl or alkenylof from C₈ to C₂₂ ; m and n are integers of from 1 to 6; q is an integerof from 2 to 4; s is an integer of from 1 to 3; Y⁻ is an anion selectedfrom the group consisting of chloride, acetate and formate.
 14. Anemulsifying system according to claim 10 wherein the emulsifying agentcomprises at least one compound selected from compounds of the formula:##STR12## wherein R₉ is an alkyl or alkenyl radical from C₁₂ to C₂₂, R₁₀is an alkyl or hydroxyalkyl radical from C₁ to C₃ -y is a chloride oracetate anion, 1 is a number equal to (3-g), g is a number 1,2 or 3, ris 0 or 1, h is (4-j) and j is 1,2 or
 3. 15. An emulsifying systemaccording to claim 14 wherein R₉ is stearyl or oleyl.
 16. An emulsifyingsystem according to claim 10 wherein the emulsifying agent B comprisesat least one compound of the formulae

    R.sub.9 --NH--(CH.sub.2).sub.3 --.sub.f --NH.sub.2 and

    R.sub.9 --(CO)--NH--(CH.sub.2).sub.3 --.sub.f --NH.sub.2

wherein f designates a number 2, 3, 4 or 5 or R₉ represents an alkyl oralkenyl radical of from C₁₂ to C₂₂.
 17. An emulsifying system accordingto claim 16 wherein R₉ is stearyl or oleyl.
 18. An emulsifying systemaccording to claim 1 additionally containing at least one thickeningagent selected from the group consisting of water-soluble organiccompounds capable, within a pH range from 3 to 9, of increasing theviscosity of a cationic emulsion of bitumen/polymer binder withoutmodifying the viscosity of the aqueous phase along of said emulsion. 19.An emulsifying system according to claim 18, wherein said thickeningagent is a water-soluble natural gum.
 20. An emulsifying systemaccording to claim 18, wherein said thickening agent is a water-solublepolyurethane of low molecular weight, formed by the reaction of apolyisocyanate with a polyester-polyol or a polyether polyol.
 21. Anemulsifying system according to claim 20 wherein the polyurethane has amolecular weight below 20,000.
 22. An emulsifying system according toclaim 18 wherein the weight of thickening agent is from 5 to 30% of thetotal weight of the combination formed by the cationic nitrogencontaining emulsifying agent, the phosphonic adjuvant and the thickener.23. An emulsifying system of claim 22 wherein the thickening agent is awater-soluble natural gum.
 24. An emulsifying system according to claim4 wherein the aromatic or alicyclic heterocycle is a pyridinic orpiperidinic heterocycle.
 25. An emulsifying system according to claim 12wherein the hydrocarboyl radical is an alkenyl or alkyl radical of fromC₆ to C₂₂ or a benzyl radical.